AU1807799A - A polysiloxane having a copolymer dispersed therein and sealants containing the same - Google Patents
A polysiloxane having a copolymer dispersed therein and sealants containing the same Download PDFInfo
- Publication number
- AU1807799A AU1807799A AU18077/99A AU1807799A AU1807799A AU 1807799 A AU1807799 A AU 1807799A AU 18077/99 A AU18077/99 A AU 18077/99A AU 1807799 A AU1807799 A AU 1807799A AU 1807799 A AU1807799 A AU 1807799A
- Authority
- AU
- Australia
- Prior art keywords
- weight
- copolymer
- polysiloxane
- percent
- sealant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 127
- -1 polysiloxane Polymers 0.000 title claims abstract description 113
- 229920001577 copolymer Polymers 0.000 title claims abstract description 75
- 239000000565 sealant Substances 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 claims abstract description 116
- 239000000178 monomer Substances 0.000 claims abstract description 110
- 229920000642 polymer Polymers 0.000 claims abstract description 73
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 9
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 21
- 239000004014 plasticizer Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000004971 Cross linker Substances 0.000 claims description 17
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012744 reinforcing agent Substances 0.000 claims description 16
- 239000004970 Chain extender Substances 0.000 claims description 15
- 230000002209 hydrophobic effect Effects 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 14
- 239000002318 adhesion promoter Substances 0.000 claims description 13
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 7
- 239000013008 thixotropic agent Substances 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 229910021485 fumed silica Inorganic materials 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- AOOAEHIAZBYEDV-UHFFFAOYSA-N n-[(butan-2-ylamino)-dimethylsilyl]butan-2-amine Chemical group CCC(C)N[Si](C)(C)NC(C)CC AOOAEHIAZBYEDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- CGRVKSPUKAFTBN-UHFFFAOYSA-N N-silylbutan-1-amine Chemical group CCCCN[SiH3] CGRVKSPUKAFTBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910018557 Si O Inorganic materials 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 3
- 238000010998 test method Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- 125000003544 oxime group Chemical group 0.000 claims 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims 2
- 239000007983 Tris buffer Substances 0.000 claims 1
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 235000010216 calcium carbonate Nutrition 0.000 description 7
- 239000004567 concrete Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000004590 silicone sealant Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000004579 marble Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229920004482 WACKER® Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000003679 aging effect Effects 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- UCVPKAZCQPRWAY-UHFFFAOYSA-N dibenzyl benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC=2C=CC=CC=2)C=1C(=O)OCC1=CC=CC=C1 UCVPKAZCQPRWAY-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920006334 epoxy coating Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229920005573 silicon-containing polymer Polymers 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- KIRJCIOJBWAUKT-UHFFFAOYSA-N 1,10-dihydroperoxydecane Chemical compound OOCCCCCCCCCCOO KIRJCIOJBWAUKT-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- AHSGHEXYEABOKT-UHFFFAOYSA-N 2-[2-(2-benzoyloxyethoxy)ethoxy]ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOCCOC(=O)C1=CC=CC=C1 AHSGHEXYEABOKT-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- ZIDNXYVJSYJXPE-UHFFFAOYSA-N 2-methylbutan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCC(C)(C)OOC(=O)CCCCCC(C)(C)C ZIDNXYVJSYJXPE-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OQGHDAKCDGEWNH-UHFFFAOYSA-M C[Sn](C)O Chemical compound C[Sn](C)O OQGHDAKCDGEWNH-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- YGHFDTDSFZTYBW-UHFFFAOYSA-N O-silylhydroxylamine Chemical class NO[SiH3] YGHFDTDSFZTYBW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- WUILYKHTEDWVOM-UHFFFAOYSA-N carboxy prop-2-enoate Chemical compound OC(=O)OC(=O)C=C WUILYKHTEDWVOM-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LZJUZSYHFSVIGJ-UHFFFAOYSA-N ditridecyl hexanedioate Chemical compound CCCCCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCCCC LZJUZSYHFSVIGJ-UHFFFAOYSA-N 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- GBFVZTUQONJGSL-UHFFFAOYSA-N ethenyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)C=C GBFVZTUQONJGSL-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HRKWOOHVRHBXHJ-UHFFFAOYSA-N hexan-2-yl prop-2-enoate Chemical compound CCCCC(C)OC(=O)C=C HRKWOOHVRHBXHJ-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- OGVVDLMGEQARAV-UHFFFAOYSA-N n-[bis(butan-2-ylamino)-methylsilyl]butan-2-amine Chemical compound CCC(C)N[Si](C)(NC(C)CC)NC(C)CC OGVVDLMGEQARAV-UHFFFAOYSA-N 0.000 description 1
- HDNXAGOHLKHJOA-UHFFFAOYSA-N n-[bis(cyclohexylamino)-methylsilyl]cyclohexanamine Chemical compound C1CCCCC1N[Si](NC1CCCCC1)(C)NC1CCCCC1 HDNXAGOHLKHJOA-UHFFFAOYSA-N 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Abstract
A high elongation, low 100% modulus composition comprises a copolymer dispersed in a continuous phase polysiloxane. The copolymer is made from high amounts of at least a monomer which is capable of forming a low Tg polymer and relatively low amounts of at least a monomer which is capable of forming a high Tg polymer. The monomer forming the low Tg polymer can be an alkyl acrylate whereas the monomers forming the high Tg polymer can be a vinyl ester, an acrylonitrile or derivatives thereof, a vinyl substituted aromatic such as styrene, an alkyl methacrylate, and the like. The composition has good adhesion to substrates as well as good viscosity aging, and can be utilized in caulks or sealants.
Description
WO99/31179 PCT/US98/25988 1 A POLYSILOXANE HAVING A COPOLYMER DISPERSED THEREIN AND SEALANTS CONTAINING THE SAME 5 FIELD OF THE INVENTION The present invention relates to a low temperature flexible, water-repellant polysiloxane containing copolymer particles dispersed therein. More specifically, the present invention relates to the copolymer particles being formed in 10 situ by polymerizing at least two different types of monomers in the polysiloxane which is curable at low temperatures; for example, an ambient temperature, upon exposure to moisture. Cured sealants containing the copolymer-polysiloxane have high elongation properties. 15 BACKGROUND OF THE INVENTION Curable polyorganosiloxane, also known as silicone compositions have been used as sealants, caulks, adhesives, and in other similar applications because of their excellent 20 water repellency, good adhesion, chemical and biological inertness, and good weather resistance. Such compositions generally contain a reactive polyorganosiloxane, crosslinking agents, and crosslinking catalysts. Polyorganosiloxane compositions are, however, relatively 25 expensive and do not always provide satisfactory physical properties such as toughness and strength. In order to improve the physical properties of polyorganosiloxane compositions, various inorganic filler materials such as silica, diatomaceous earth, calcium carbonate, iron oxide 30 and the like have been added. The use of such additives, however, has often resulted in an undesirably high viscosity which adversely affects the ease of application of the composition. In order to reduce the viscosity of filled polyorganosiloxane compositions to an acceptable level, 35 organic solvents or non-reactive organosiloxanes can be used. However, this can result in undesirable shrinkage, or the release of environmentally undesirable organic WO 99/31179 PCTIUS98/25988 2 components into the atmosphere or staining problems due to the non-reactive siloxane extrudate. U.S. Patent No. 4,138,387 to Bluestein relates to a polyolefin filled-organo polysiloxane composition which 5 are allegedly stable dispersions comprised of a continuous phase of essentially ungrafted organo polysiloxane and a discontinuous phase of finely divided solid particles of a homopolymer or copolymer prepared from an organic monomer or monomers. The composition, however, is generally 10 unacceptable as a sealant inasmuch as it has low elongation such as a maximum of only about 190 percent. SUMMARY OF THE INVENTION Curable dispersed copolymer-polysiloxane 15 compositions are prepared by the in situ free radical polymerization in a polysiloxane fluid of at least two different classes of monomers, e.g. a first class of monomers which are capable of forming a polymer having a low Tg and a second class of monomers which are capable of 20 forming a polymer having a high Tg. The copolymer, which can be either a thermoplastic or a thermoset, is generally a dispersed phase in the form of particles, the surface thereof generally having substantially high Tg polymers. The use of small amounts of a thixotrope renders the 25 dispersed copolymer polysiloxane composition non-slump. The composition is generally viscous and is moisture curable. Utilization of the two different classes of monomers yields synergistic results upon cure in that the dispersed copolymer-polysiloxane composition has very high elongation 30 as well as a 100% modulus of less than 50 psi. The composition also exhibits good flexibility and excellent weathering. Unlike previous reinforcing filler technology, the in situ polymerized particles have the unique characteristics of both reinforcing (strengthening) as well 35 as plasticizing (increasing elasticity) the cured silicone WO99/31179 3 PCT/US98/25988 network. Another attribute of the composition of the present invention is that they have good viscosity aging resistance before cure. Accordingly, the composition is suitable for use as a binder in caulks and sealants. 5 DETAILED DESCRIPTION OF THE INVENTION COPOLYMER-POLYSILOXANE The dispersed copolymer-polysiloxane compositions of the present invention are generally made by reacting two 10 or more different monomers in the presence of a polysiloxane fluid. The polysiloxane fluid generally contain a total of two or more reactive functional groups on the polymer chain, preferably at the terminal portion thereof. The polysiloxane fluid desirably is an organo 15 polysiloxane of the formula R 20 CR) 3m (X),m Si-O -i- O Si (X) (R) 3m
R
2 n 25 where R' and R 2 , independently, is an alkyl having from 1 to 8 carbon atoms, desirably from 1 to 4 carbon atoms with methyl being preferred, or is an aromatic group or substituted aromatic group having from 6 to 10 carbon atoms with phenyl being preferred, and "n" is such that the weight 30 average molecular weight of the polysiloxane is from about 2,000 to about 200,000 and desirably from about 15,000 to about 80,000 grams/mole. It is to be understood that the above polymers also contain, as noted above, two or more reactive functional groups (X) therein. The functional 35 groups, independently, can be OH, or OR , or N(R 4
)
2 , or WO 99/31179 4 PCT/US98/25988
CH
2 0 -- O--C (enoxy) , or --- C-R' (acyloxy), or
R
7 5
R
9 Ru / / --O--N=C (oximo), or -- O0--N (aminoxy), 10 R 12
R"
0
RR
s 0 15 or an-N-C-R 6 group, where R 3 through R 12 , are, independently, an alkyl having from about 1 to about 8 carbon atoms. The amount of the functional groups, i.e. m, is 1, 2, or 3. The one or more R groups, independently, is an alkyl having from 1 to 8 carbon atoms or an aromatic or an alkyl-aromatic 20 having from 6 to 20 carbon atoms and optionally containing one or more functional groups thereon such as amine, hydroxyl, etc. A polysiloxane fluid can furthermore contain a blend of two or more different polysiloxanes and/or polysiloxanes having different viscosities. The 25 polysiloxanes are generally a viscous liquid and are commercially available, e.g. Masil" SFR 6,000 from PPG Corporation and Wacker 6LV from Wacker Corporation. The organopolysiloxane fluid generally constitutes a reactive continuous phase containing a discontinuous phase 30 therein which comprises copolymer particles made in situ by free radical polymerization. Desirably, two or more, and preferably two types of monomers are utilized wherein one, if homopolymerized, forms a low Tg polymer and the other, if homopolymerized, forms a high Tg polymer. As noted above, 35 the copolymer can either be a thermoplastic, or if crosslinked, a thermoset. The one or more monomers utilized which otherwise would form a polymer having a low Tg, i.e. generally from about -70 0 C to about 0 0 C and desirably from about -550C to 40 about -10 0 C, include the various alkyl acrylates, and the like. The alkyl acrylate monomers generally have an alkyl WO99/31179 5 PCTIUS98/25988 portion which contains from 1 to 18 carbon atoms, and desirably from 1 to 8 carbon atoms. Examples of such suitable acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, 5 isobutyl acrylate, 1-ethyl propyl acrylate, 1-methyl pentyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexly acrylate, and the like, with n-butyl acrylate being highly preferred. A small amount of approximately 20 percent or less and desirably from about 2 to 8 percent by weight of 10 the various alkyl acrylates can contain functional groups thereon. Such groups include hydroxyl, epoxy, acetoacetyl, acrylamide, and the like, are preferably terminal groups and serve to improve adhesion to various substrates such as metals, concrete, wood, etc. 15 One or more monomers are also utilized which otherwise would form a polymer having a high Tg, i.e. generally from about 1 0 C or SoC to about 150 0 C and desirably from about 20 0 C to about 120 0 C. Such monomers include vinyl esters, acrylonitrile or derivatives thereof, vinyl 20 substitute aromatics, alkyl methacrylates, vinyl chloride, vinylidene chloride, and the like. The non-vinyl portion of the vinyl ester generally contains a total of from 2 to about 10 carbon atoms, desirably from about 2 to about 8 carbon atoms with acetate, i.e. vinyl acetate, being highly 25 preferred. With respect to the acrylonitrile monomers, while the same is generally utilized, alkyl derivatives thereof containing from 1 to about 6 carbon atoms such as methyl acrylonitrile, ethyl acrylonitrile, etc. can also be utilized. The vinyl substituted aromatics generally contain 30 from 8 to about 12 carbon atoms and specific examples include styrene, alpha-methyl styrene, vinyl toluene, and the like. The alkyl methacrylates include monomers wherein the alkyl group contains from 1 to 18 carbon atoms, and desirably from 1 to 8 carbon atoms. Specific examples 35 include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, ethyl hexyl methacrylate, and the like, with methyl WO99/31179 6 PCT/US98/25988 methacrylate, being preferred. Of the various one or more monomers which are capable of forming a polymer having a high Tg, the vinyl esters are preferred, such as vinyl acetate inasmuch as it has a reactive ratio with the various 5 acrylate monomers such that a large portion of the vinyl acetate monomers polymerize after the various acrylate monomers have polymerized. The copolymer particles are generally formed by polymerization at the same time, for example, 10 simultaneously, the low Tg polymer forming monomers and the high Tg polymer forming monomers in the presence of the organopolysiloxane fluid. The type of copolymer will generally depend upon the reactivity ratios of the particular monomers. Reactivity ratios are defined in the 15 Polymer Handbook, second edition, by J. Brandrup and E. H. Immergut, editors, 1975. If the amount and reactivity ratios of the monomers is decidedly different, the copolymers formed will initially be rich in the more reactive monomer until the more reactive monomer is 20 consumed. Then the resulting copolymer portion formed will subsequently or terminally be rich in the less reactive monomer. If the reactivity ratios are similar, a random copolymer will generally be formed. Moreover, if the high Tg polymer forming monomer has a reactivity ratio similar to 25 that of the low Tg polymer forming monomer, it is then desirable to add a large portion of the high Tg polymer forming monomer in a second or subsequent stage so that the copolymer particles be surface rich in the high Tg polymer. During the formation of the copolymers, small amounts of 30 low Tg homopolymer and of high Tg homopolymer will also be formed. The weight of high Tg polymer forming monomers can vary from about 2.5 percent to about 50 percent and desirably from about 20 percent to about 40 percent by weight (based upon the total weight of monomers, i.e. high 35 and low forming the copolymer particles). Although a majority of the repeat units in the copolymer will be derived from low Tg monomers, desirably ... . ...... . ... . .. ne m WO 99/31179 7 PCTIUS98/25988 the copolymer particles have a majority or are phase rich on the surface thereof with repeat units in the copolymer and/or homopolymers derived from high Tg monomers. One manner of forming such particles is to add a significant 5 amount such as from about 50 to about 100 percent by weight (i.e. from about one-half to all) of high Tg forming monomers during a late stage or a second stage of the polymerization. By late stage or second stage polymerization it is meant that some or most of the high Tg 10 forming monomers are added after a certain or specified amount, for example, at least about 60 percent, desirably at least about 70 percent, and preferably at least about 80 percent of the previously added monomers (e.g. mostly low Tg forming monomers) have been polymerized. 15 Regardless of the monomer weight ratio, it is generally thought that the surface composition of the dispersed thermoplastic copolymer particles, have a high Tg, e.g. greater than about 50C and preferably greater than about 20 0 C. Otherwise viscosity aging sensitivity would often 20 render the polysiloxane composition generally unsuitable for non-slump sealant applications. Whether the surface Tg of the copolymer particles have a desired high Tg can be determined by the use of various methods or apparatus such as by atomic force microscopy, through the use of solid 25 state nuclear magnetic resonance or through ESCA, i.e. electron spectroscopy for chemical analysis. Moreover, it has also been found that the interior of the dispersed copolymer particles should not exceed a Tg of zero degrees centigrade and desirably not above minus 30 10 0 C. Thus, the dispersed phase contains copolymer particles predominantly having high Tg polymers on the surface thereof and low Tg polymers in the interior thereof. The surface of the particles need not contain solely the high Tg polymer thereon and the same may exist as a partial coating, as 35 particles, aggregates, etc., thereon, and the like. Moreover, the dispersed phase will at times contain small amounts of the organopolysiloxane or grafted WO99/31179 8 PCT/US98/25988 polyorganosiloxane therein. Conversely, the continuous organopolysiloxane phase can contain some high and/or low Tg polymer-grafted polysiloxanes therein. The shape of the dispersed copolymer particles can 5 vary but generally is spherical or nearly spherical with the size thereof ranging from about 5 or 10 microns up to about 50, 30, or 20 microns in diameter. The size distribution of the dispersed particles is usually not monodisperse. The weight percent of the discontinuous phase, 10 i.e. the phase containing substantially copolymers, e.g. copolymers derived from one or more high Tg forming monomers, and one or more low Tg forming monomers is from about 10 or 20 to about 85 percent and preferably from about 50 to about 75 percent by weight based upon the total weight 15 of the discontinuous phase and the continuous polysiloxane phase. The utilization of the dispersed copolymer particles having a surface Tg of at least 5 0 C and preferably at least 20 0 C and a lower Tg interior in a polysiloxane fluid 20 unexpectedly yields a composition which has good viscosity aging resistant properties. That is, upon standing at ambient temperature, the viscosity increase of the dispersed copolymer-polysiloxane composition before cure is little or small. Thus, the compositions do not have a viscosity 25 increase such that they become an elastic material. Suitable viscosity aging properties include an increase of viscosity of generally less than 100%, desirably less than 50%, and preferably less than 25%, after aging for 24 hours at ambient temperature, i.e. 20'C, in accordance with ASTM 30 D2452-75. The dispersed copolymer-polysiloxane composition of the present invention also has unexpectedly been found upon cure to yield high elongations at break, such as at least 300 percent or 400 percent, desirably at least 500 or 35 600 percent, and preferably at least 700 or 800 percent up to about 1,100 percent at 20 0 C. Moreover, the 100% tensile strength modulus is from about 10 to about 50 psi. -----------------------. .. i F- WO99/31179 9 PCTIUS98/25988 The copolymer forming monomers are polymerized in the presence of a free radical initiator. Desirably, various initiators are utilized which are soluble in the monomers such as azo and desirably organic peroxide 5 initiators. Examples of suitable organic peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dialkyl peroxides such as di-tertiary-butyl peroxide and dicumyl peroxide; hydroperoxide and decylene hydroperoxide; cyclic peroxides such as 1,5-dimethylhexane-1,5-peroxide; peresters 10 such tert-butylperbenzoate, tert-butyl-peroxy isopropyl carbonate, tert-butylperoctyate and tert-butylperacetate. Examples of azo compounds include azobisisobutyronitrile, 2
,
2 -azobis-2,4-dimethylvaleronitrile, 2-carbamoyl, azoisobutylonitrile, dimethyl-2,2'-azobisisobutylate and 15 l,1-azobiscyclohexane carbonitrile. Generally, various persulfates are not utilized inasmuch as they are aqueous catalysts and are not soluble in the copolymer forming monomers of the present invention. The amount of the initiators is generally from about 0.05 to about 5.0 parts 20 by weight for every 100 parts by weight of all of the low Tg and high Tg polymer forming monomers. The polymerization temperature will vary depending upon the particular monomers utilized, but generally is from about 60 0 C to about 130 0 C and preferably from about 70 0 C to 25 about 100 0 C in order to insure a quick reaction. The actual in situ polymerization of the copolymer can proceed in any desired manner. A preferred mode of polymerization involves adding an organo polysiloxane to a reaction vessel which is free of oxygen, e.g. a nitrogen 30 atmosphere. A mixture of the two or more monomers with at least one monomer capable of forming a low Tg polymer and a different monomer capable of forming a high Tg polymer, as well as initiators, are metered into the reaction system which has previously been heated to the polymerization 35 temperature. Polymerization then occurs with the contents of the reaction vessel being mixed utilizing any conventional mixing device so that the formed copolymer WO99/31179 10 PCTIUS98/25988 particles are dispersed as a separate phase within the polysiloxane which exists generally as a continuous phase. Polymerization as well as the addition of monomers thereto is continued until a suitable amount of dispersed copolymer 5 particles have been formed. Optionally, one or more crosslinking compounds having more than one polymerizable unsaturated olefinic groups such as divinyl benzene, allylmethacrylate, and the like, in amounts of up to 5 parts by weight, desirably from 10 about 0.1 to 2 parts by weight, and preferably from about 0.1 to 0.5 parts by weight for every 100 parts by weight of the copolymer forming monomers can be used, provided that severely agglomerated or irregularly shaped particles are not formed in amounts sufficient to render the dispersion 15 too viscous or unstable. Another important aspect of the present invention is the utilization of low amounts of a thixotropic agent such as generally less than 3 parts by weight, desirably from about 0.05 to about 2 parts by weight, and preferably 20 from about 0.05 to about 0.5 parts by weight per 100 parts by weight of the dispersed copolymer-polysiloxane composition. Examples of suitable thixotropic agents include hydrogenated castor oil, fumed silica, precipitated calcium carbonate, and the like. The above-noted amounts of 25 thixotropic agents result in a non-slump composition, i.e. non-sagging in vertical joints as measured by ASTM D 2202 938. The dispersed copolymer-polysiloxane compositions of the present invention, are cured by generally subjecting 30 them to moisture. Either a conventional one-component or two-component cure system can be utilized. In a conventional one-component cure, the polysiloxane is converted to a compound having an alkoxy, an oxime, an enoxy, an amido, an amino, or an acetoxy blocking group in a 35 manner well known to the art and to the literature. Conventional condensation catalysts are utilized such as an organo tin, for example, dibutyltin diacetate, dibutyltin WO99/31179 11 PCTIUS98/25988 dilaurate, or dimethylhydroxytin oleate, or an organo titanate. Optionally, the blocked one-component cure system can contain crosslinking agents as set forth herein below. In a two-component cure system, crosslinking agents such as 5 a multi-functional alkoxy silane or oligomers thereof and catalysts are kept separate from the polysiloxane until reaction. The amount of catalyst for the two component system, is generally much higher than in the one component system. Such cure systems are well known to the art, e.g. 10 see Rubber Technology, 3rd Edition, pp. 406-07, 1987, by Maurice Morton, Van Nostrand Reinhold, which is hereby fully incorporated by reference. While a variety of conventional crosslinkers are suitable, oxime crosslinkers are preferred, such as 15 for example, vinyl tris-methylethylketoximosilane, and methyltris-methylethylketoximosilane. Methyltris methylethylketoximosilane (MOS) is available under the trade name OS-1000 from Allied Signal Corp. Other crosslinkers are also suitable; such as for example, 20 alkoxysilanes, epoxyalkylalkoxysilanes, amido silanes, aminosilanes, enoxysilanes and the like, such as tetraethoxysilanes, methyltrimethoxy silane, vinyl trimethoxysilane, glycidoxypropyltrimethoxsilane, vinyl tris-isopropenoxysilane,methyl tris-isopropenoxysilane, 25 methyl tris-cyclohexylaminosilane, and methyl tris secondarybutylaminosilane. Mixtures of crosslinkers can also be employed. The amount of the crosslinking agent is generally from about 0.2 to about 20 parts by weight, desirably from about 1 to about 10 parts by weight, and 30 preferably from about 1.5 to about 6.5 parts by weight for every 100 parts by weight of said copolymer-polysiloxane. Another important aspect of the present invention is that various compatibilizing agents are optionally utilized to generally form a thin layer which compatibilizes 35 the generally otherwise incompatible polysiloxane with a dispersed high Tg-low Tg polymer phase and thus helps control the particle size, improve tensile strength WO99/31179 12 PCT/US98/25988 properties, and result in lower dispersion viscosities. Suitable compatibilizing agents include vinyl containing or mercapto containing polyorganosiloxanes, or macromonomers such as monomethacryloxypropyl terminated 5 polydimethylsiloxane, and the like, with vinyl terminated polydimethyl siloxane such as PS443 from United Chemical Technologies, Inc. being preferred. The amount of the optional compatibilizing agents are generally up to about 15 parts by weight, and desirably from about 1 to about 5 parts 10 by weight for every 100 parts by weight of the high and low Tg polymer forming monomers. The dispersed copolymer-polysiloxane composition generally has a low viscosity which permits it to be readily extruded. Thus, the copolymer-polysiloxane can be used in 15 low temperature applications. Upon exposure to moisture, the composition cures and forms a low temperature flexible, water repellant, thermal oxidative resistant, UV resistant material. The composition also upon cure has low shrinkage and is soft and pliable. Unexpectedly, the dispersed 20 copolymer-polysiloxane composition has synergistic elongation properties at break as noted above of from about 300 to about 1,100 percent and yet has low 100% tensile modulus properties, the combination of which is highly desired for sealant properties. These properties were 25 unexpected inasmuch as polysiloxane compositions made from only low Tg forming monomer(s) or from only high Tg forming monomer(s) such as those contained in conventional silicone sealants generally had low elongations, typically less than 300 percent. 30 SEALANT Sealant compositions which are particularly useful as caulks, are comprised of the dispersed copolymer polysiloxane, one or more of the above noted crosslinkers, and optionally though preferably: an adhesion promoter; a 35 reinforcing agent; a chain extender; and a plasticizer. The sealants in their uncured states have little sag, generally less than about 1.0 inches, desirably less than about 0.5 WO 99/31179 13 PCT/US98/25988 inches, preferably less than about 0.2 inches, most preferably about 0. The uncured sealants are easy to tool and have a tooling life of from about 5 to about 240, desirably from about 10 to about 180, and preferably from 5 about 20 to about 150 minutes. Once the sealant cure is initiated, the sealants become tack free in generally about 0.5 to about 12 hours, desirably from about 1 to about 8 hours, and preferably from about 1.5 to about 7 hours. The sealants become substantially cured, i.e. 10 chemically crosslinked, in about 7 days although this may vary depending upon the curing system, particularly the catalyst employed. The sealants are typically completely cured at about 21 days at 25 0 C and 50% relative humidity. The cured sealant has a shore A hardness 15 generally from about 3 to about 45, desirably from about 8 to about 35, and preferably from about 10 to about 25; a tensile strength generally from about 20 to about 400, desirably from about 50 to about 300, and preferably from about 60 to about 200 psi; an elongation to break of 20 generally from about 250 to about 1600, desirably from about 350 to about 1400, and preferably from about 400 to about 1200 percent; and a 100% extension modulus of generally from about 8 to about 130 psi, desirably from about 10 to about 100 psi, preferably from about 10 to 25 about 50 psi, and most preferably from about 15 to about 35 psi. The extension modulus is measured according to ASTM D412 at 100% elongation. The amount of the adhesion promoter in the sealing composition is generally from 0 to about 15, 30 desirably from about 0.3 to about 15, preferably from about 0.75 to about 6, and more preferably from about 1 to about 3 parts by weight based upon 100 parts by weight of the copolymer and polysiloxane. The amount of the reinforcing agent is generally from 0 to about 100, desirably from 35 about 0.1 to about 100, preferably from about 0.1 to about 60, and more preferably from about 0.2 to about 30 parts by weight based upon 100 parts by weight of the copolymer and WO99/31179 14 PCT/US98/25988 the polysiloxane. The amount of the plasticizer is from 0 to about 80, desirably from about 5 to about 80, and preferably from about 10 to about 30 parts by weight based upon 100 parts by weight of the copolymer and the 5 polysiloxane. The amount of the chain extender is generally from 0 to about 12, desirably from about 0.2 to about 12, preferably from about 0.2 to about 8, and more preferably from about 0.5 to about 5 parts by weight based upon 100 parts weight of the polysiloxane. 10 The plasticizer contributes to the flexibility, particularly low temperature flexibility, of the cured sealant. Unexpectedly, the addition of the plasticizer unlike conventional polysiloxanes which result in reduced tensile strength, imparts improved tensile strength to the 15 copolymer-polysiloxane admixture. The plasticizer also modifies the modulus of the cured sealant; if modulus values exceed about 100 psi at 100% extension, the cured sealant tends to pull the surface of the material, particularly materials like concrete, to which the sealant 20 is applied. The modulus values of the cured sealant are preferably less than about 60 psi, more preferably less than about 40 psi. The plasticizer generally has a number average molecular weight of from about 100 to about 800 and 25 desirably from about 200 to about 400. Preferably the plasticizer has a boiling point greater than about 100 0 C, at 1 atmospheric pressure. Suitable plasticizers are phthalate esters, dibenezoate esters, phosphate esters, and adipate esters. Examples of phthalate esters are dibutyl 30 phthalate, dioctyl phthalate, dimethyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, texanol benzyl phthalate, C 7 benzyl phthalate, and C 9 benzyl phthalate. Examples of dibenzoate esters are dipropylene glycol dibenzoate, polypropylene gylcol dibenzoate, 35 diethylene glycol, and triethylene glycol dibenzoate. Examples of adipate esters are dioctyl adipate, ditridecyl adipate, and dialkyl adipate. Examples of phosphate esters WO99/31179 15 PCTIUS98/25988 are tricryesyl phosphate, trioctyl phosphate, triphenyl phosphate, and t-butylphenyl diphenyl phosphate. Other suitable plasticizers are for example terephthalates such as 1,4-benzenedicarboxylates, and trimelliatics such as 5 1,2,4-benzenedicarboxylates. A suitable butyl benzyl phthalate, a phthalate ester of butyl alcohol and benzyl alcohol, is commercially available as Santicizer 160 formerly from Monsanto Solution Company, St. Louis, Missouri, now Solutia St. Louis, Missouri. 10 The chain extenders are difunctional molecules which extend the length of the polysiloxane polymer chains and modify the modulus of elongation of the cured sealant. Suitable classes of chain extenders are silane chain extenders such as amino silanes, amido silanes, acetoxy 15 silanes, and aminoxy silanes. Suitable chain extenders are for example, methylvinyl bis-N,-methylacetamidosilane, methylhydrogendiacetoxysilane, dimethylbis diethylhydroxylaminosilane and dimethylbis secondarybutylaminosilane. Dimethylbis-secondary 20 butylaminosilane is available under the trade name SB-72 from Wacker Silicones of Adrian, Michigan. The adhesion promoter, although optional, is highly preferred; the adhesion promoter provides the sealant with long term adhesion to the substrate. Suitable 25 classes of adhesion promoters are aminoalkyl, mercaptoalkyl, epoxyalkyl, ureidoalkyl, carboxy, acrylate and isocyanurate functional silanes. Examples of suitable adhesion promoters are mercaptopropyltrimethoxysilane, glycidoxpropyltrimethoxysilane, aminopropyltriethoxysilane, 30 aminoethylaminopropyltrimethoxysilane, ureidopropyltrimethyloxysilane, bis-y-trimethoxysilyl propylurea, 1,3,5-tris-y-trimethoxysilylpropylisocyanurate, bis-y-trimethoxysilylpropylmaleate and fumarate and y methacryloxypropyltrimethoxysilane A suitable silane 35 adhesion promoter is aminopropyltriethoxysilane which is available under the trade designation A-1100 Silane from OSi, a division of Witco Corporation.
WO99/31179 16 PCT/US98/25988 The reinforcing agents are optional although highly preferred, particularly when the sealant is used as a caulk. Reinforcing agents increase tensile strength in the cured sealant and reduce sag of the uncured sealant. 5 The reinforcing agent also functions as a thixotrope. Such reinforcing agents are finely divided particulates and include both the conventionally known reinforcing agents and semi-reinforcing agents, typically having a particle size less than about 10 microns, preferably about 5 microns 10 or less, more preferably about 0.1 microns or less. Suitable reinforcing agents include hydrophobic treated fumed silicas, such as TS 720 from Cabot Corporation, or R 972 from Degussa Corporation, hydrophobic precipitated calcium carbonates, talc, zinc oxides, and polyvinyl 15 chloride powders. Other ingredients can also be utilized in the sealant formulation in amounts up to about 20 parts by weight and desirably from about 0.01 to about 15 parts by weight per 100 parts by weight of the copolymer and the 20 polysiloxane. Such ingredients include fungicides. Moreover, extender fillers such as ground calcium carbonates and diatomaceous earth are optionally employed. Such extenders have minimal or no reinforcing effect and/or minimal or no thixotropic effect. 25 UV stabilizers can be optionally added. Pigments or colorants such as titanium dioxide, iron oxide, carbon black are optionally employed to impart color to the sealant and/or to act as ultraviolet stabilizer. LTV inhibitors, anitozonates are also optionally added. 30 The sealant in its uncured state may optionally contain solvents such as organic solvents to reduce the viscosity; such solvents are employed where the sealant is to be used as a coating such as for a roof. Such solvents are less preferred where the sealant is to be used as a 35 caulk since as such solvents evaporate, the cured sealant shrinks which is not desirable.
WO99/31179 17 PCTIUS98/25988 The present invention relates to a family of silicone sealants which generally meet all of the performance features demanded by the construction industry for joint and general sealing such as; non-staining 5 characteristics on porous substrates like white marble, virtually no change of properties during weather exposure, low modulus elastomeric behavior to accommodate joint movement without adhesive or cohesive failure, extended tooling life which allows a worker to apply the sealant in 10 long joints before having to tool the surface of the sealant and primerless adhesion to a broad spectrum of substrates such as anodized aluminum, concrete, brick, mortar, marble, granite, limestone, porcelain, glass, painted surfaces, wood, PVC, polyacrylate, polycarbonate, 15 and polystyrene, etc. Unlike conventional silicone sealants wherein the tooling time generally ranges from about 2 to about 30 minutes and even less at elevated temperatures and humidities, for example, from about 1 to about 10 minutes, 20 the copolymer-silicone sealants of the present invention can generally have tooling times in excess of 2 hours. As noted above, the copolymer-silicone sealant compositions of the present invention have good low modulus characteristics such as low as 10 to 20 PSI at 100 percent extension. 25 Conventional silicone sealants generally do not have such a high elongation with extreme low modulus and can fail on weak tensile stress surfaces such as concrete. With proper compounding, the copolymer polysiloxane compositions of the present invention can also 30 be used to coat fabrics, or to form gaskets. Another large area of utility is as silicone alloys, including thermoset alloys such as RTV (room temperature vulcanizable) silicone acrylate alloys, molded silicone rubbers, and silicone acrylate epoxy additives wherein the silicone can be the 35 copolymer- polysiloxane composition of the present invention or it can be a mixture or blend of a conventional silicone and the copolymer-polysiloxane composition of the present WO99/31179 18 PCT/US98/25988 invention. The composition of the present invention can also be used in medical applications, electronic applications, automotive applications, textile applications, paper coatings, polishes, cosmetic applications, 5 pharmaceutical applications and as processing aids. EXAMPLES Polymerization Set-Up: 10 The reactor used for polymerization was a 5-neck jacketed 2 liter resin kettle, fitted with a mechanical stirrer, a condenser, a nitrogen-inlet, a vacuum port and a safety release valve. The monomer/initiator mixture was stored in a 15 graduated cylinder, which was refrigerated and was kept under a gentle nitrogen sweep. The feeding was done from the bottom of the reactor and the rate of which was controlled by a metering pump. To heat the reactor to the desired temperature, a 20 knife-heater was installed in the circulation loop of polysiloxane (non-reactive) fluid, which was pumped to flow through the jacket of the reactor. A temperature-control console monitored the temperature of the thermocouple located at the bottom of the reactor and controlled the 25 timing of opening and closing of a diaphragm valve. The diaphragm valve was installed to control the flow of the cool polysiloxane fluid into the heating loop, such that the exotherm of the polymerization could be counteracted. Four additional temperature readouts updated the temperatures of 30 reactor inlet, reactor outlet, monomer/initiator reservoir and polysiloxane bath. The thermo-couple inside the reactor was located at the bottom of the resin kettle about one-half inch below the monomer inlet. The agitation was accomplished by specially 35 designed blades, which have two two-leafed marine blades, about 3 inches apart along the stainless steel shaft and two sweeping blades which keep the material on the interior wall WO 99/31179 19 PCT/US98/25988 moving. In order to facilitate the mixing of the incoming monomer in the vicinity of the monomer inlet, two small slanted blades at the foot of each sweeping blade were also provided. The speed of stirring was controlled by a 5 variable speed electric motor. The stirring speed and the torque exerted on the stirring shaft were constantly displayed by a digital readout. General Polymerization Procedure: The weighed monomer/initiator mixture was poured 10 into the refrigerated reservoir via a funnel. The contents were then kept under a nitrogen sweep. The polysiloxane fluid was weighed and placed in the reactor. The stirring speed was set at 100 rpm. The reactor was evacuated to rid it of oxygen. Then, the inside 15 temperature was brought to the desired polymerization temperature. When the temperature was 75 0 C, the monomer/initiator was fed into the reactor via a metering pump according to a pre-determined rate. 20 After the monomer addition was completed, the temperature was raised to 90 0 C and the polymerization continued for 2 hours. The final phase of the polymerization was carried out by first injecting 0.02 phr of Lupersol 575 initiator to 25 the reactor, raising the reactor temperature to 100oC, and then starting the vacuum stripping for 1 hour. The residual monomer can be effectively reduced to very low levels, either by using a high temperature activated initiator as part of the initiator package or by 30 using a booster shot of initiators during the final phase of the polymerization. Vacuum stripping will aid the efficiency of monomer removal. Utilizing the above procedures, polysiloxane compositions were produced from the recipes set forth in 35 Table I, wherein the parts are by weight.
WO 99/3 1179 PCT/US98/25988 20 'IT 0 0 ~ r- I- - r-4 0~ ~~~~ 0 c - lrN 0 -e ' u 07 7 0f t0 0j WO099/31179 PCTIUS98/25988 21 6. 0 di0 0 0u 0 0 u .0 Q) 0 UU U- E U o2 o .00 GJ 0 0 C) r_ 0 E .0 C0 0i E~ u- 1 C/) . o- 3 0 CLd 0n 4;C> - 9 0 H ~. r-' ~ - di a(i~ -C~0 0 r- ud o Ir.- - o- 0 ci c - - - ~~C.E 0 i c O~ C -Z: tCo dit0Ai, ~ 0 Mi 0 di 0~L 0. " d iC . 2 di u 0 0 N 00 E >~ > - mu w- V - - - -- U)U WO 99/31179 PCT/US98/25988 22 After the copolymer-polysiloxane composition is made, various amounts of a thixotrope, i.e. TS 720 (fumed silica) from Cabot Corporation are added thereto. The data set forth in Table II is with regard to uncured properties 5 with the exception of the tensile properties which relate to a cured copolymer-polysiloxane. These tensile properties were obtained after curing the copolymer-polysiloxane composition with 4 parts by weight of MOS per 100 parts by weight of the copolymer-polysiloxane composition in the 10 presence of 0.08 parts by weight of dibutyltin dilaurate catalyst. TABLE II Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Thixotrope TS720 (phr) 0.215 0.142 0.532 0.314 0.122 0.304 Uncured Data Flow Rate: (seconds to extrude 20 gms of polysiloxane composition) ASTM Test # D2452-75 Fresh Sample @ 60 psi 47 44 35 38 38 26 @ 20 psi 235 198 182 174 200 123 1 Day Aged Polysiloxane Composition @ 60 psi 215 51 38 41 39 87 @ 20 psi 1289 232 199 189 226 1401 1 Wk Aged Polysiloxane Composition @ 60 psi 780 49 44 40 36 969 @ 20 psi 4400 216 219 203 236 4200 Cured Tensile: Elongation % 703 1050 701 1048 848 1012 Modulus @ 100% (psi) 26 20 20 22 24 17 Strength @ Break (psi) 116 168 153 224 168 138 Uncured Viscosity Aging yes No no No no yes Sensitivity 15 Although Table II relates to the use of a thixotrope, examples not utilizing a thixotrope resulted in similar uncured properties. As apparent from Table II, only Examples 1 and 6 resulted in poor viscosity aging. For WO99/31179 PCT/US98/25988 23 example, the time to extrude 20 grams increased more than one order of magnitude for Examples 1 and 6 when aged one week, while Examples 2-5 only experienced slight increases in time to extrude 20 grams under the same aging conditions. 5 Example 1 had poor viscosity aging inasmuch as no vinyl acetate, (i.e. a high Tg forming monomer) was utilized. In Examples 2-5, wherein vinyl acetate was utilized which yields a very high Tg polymer, and yet has a low reactivity ratio so that it is located generally on the surface of the 10 particles, good viscosity aging properties were obtained. Although vinyl acetate was utilized in Example 6, the amount thereof is thought not to be sufficient to form a surface rich high Tg polymer on the copolymer particle. The amount of vinyl acetate in Example 5 can be distinguished from 15 Example 6 because additional vinyl acetate was added in a second stage in Example 5. In a similar manner, as set forth above, recipes 7 through 14 as set forth in Table III, were polymerized to form other polysiloxane compositions of the present 20 invention. ------------------------... . I - WO099/31179 PCTIUS98/25988 24 0n 00 0 C) C -00 C - 0 e~0 0 ~ 0 0 0 0 0 0 0 00 -n - un 0 0C 0 0D 0D 0D 0 0D 0 0 00 00 000 0 CD 0U- 0 0 0 0 0 - 0 - U U .~ .W 2c 5-. E v v GJ - -~ c - u WO 99/31179 25 PCT/US98/25988 C L; C..) kC.. r- r4 UU c E r4 7 7 ou u ol C..) -~~~~ 4 N ( t*
C
=
E
71U 030 - WO99/31179 PCT/1US98/25988 26 Compositions formed were tested with regard to viscosity aging sensitivity and the results thereof are set forth in Table IV. The flow rate and the viscosity aging sensitivity data relate to uncured compositions containing 5 the copolymers dispersed in the polysiloxane whereas the tensile data relates to cured compositions which were cured in a manner identical to Table II.
WO 99/31179 PCT/US98/25988 27 C' ~ ~- 00 0 (N en z -1 tr) - C -it Ko a) r N0 - 0 a' ~o8q ~oo ~6 C o (N (Na E u *~M CO C co 0 0 C-) ~ r4 0E C ci~ ct~ 2 --------------------- <.-E.
WO99/31179 PCT/US98/25988 -28 The Examples 7-11 compositions of Table III generally utilized a two stage polymerization wherein significant amounts of vinyl acetate was added in the second 5 stage, thus generally resulting in a copolymer surface rich in a high Tg polymer. Examples, 12, 13, and 14 which did not utilize vinyl acetate in the second stage did not have good viscosity aging properties. Example 15 relates to the use of a polysiloxane 10 composition of the present invention, i.e. Example 2, which was utilized as an additive in an epoxy coating. EXAMPLE 15 Parts by Weight: EPON 828 90 Example 2 10 MOS 0.35 Diethylene Triamine 3.75 N-aminoethyl piperazine 11.0 y-aminopropyltriethoxysilane 0.05 TS 720 0.05 The above ingredients were thoroughly mixed and 15 the cured at ambient temperature. The composition of Example 15 relates to an epoxy coating having improved toughness and water repellency. The epoxy coating can be applied to various substrates such as concrete, metal, wood, and the like. 20 EXAMPLE 16 An acrylate terpolymer suspension was polymerized in the presence of a silanol terminated dimethylpolysiloxane polymer, to provide a dispersed copolymer-polysiloxane composition having 70% soft 25 acrylate polymer and 30% silanol terminated dimethylpolysiloxane. A dispersed copolymer-polysiloxane composition, Example 16, was prepared from the following ingredients. ..... ..... .... - m ne% WO 99/31179 PCT/US98/25988 -29 Ingredients Total Weight e t Percent 2450 cps Silanol Terminated 300 grams 29.83 Dimethylpolysiloxane 300 grams 29.83 Vinyl Acetate 102.2 10.16 n-Butyl Acrylate 517.6 51.47 Methyl Methacrylate 66.6 6.62 N-t-Butyl Acrylamide 3.3 0.33 1000 cps Vinyl Terminated Dimethylpolysiloxane Polymer 13.7 1.36 t-amyl Peroxyneodecanoate (546-M75) 1.47 0.15 t-amyl Peroxy-2-Ethylhexanoate 0.84 0.084 (575-M75) 0.84 0.084 Total 1005.713 100.00 Chaser a Lupersol 546-M75 1 Lupersol 575-M75 2 Chaser b Lupersol 546-M75 1 Lupersol 575-M75 2 Chaser c Lupersol 575-M75 2 To a clean 2 liter reactor was added 240 g of 2000 cps reactive silanol terminated dimethylpolysiloxane 5 and 60 g of 6000 cps reactive silicon polymer to yield a mixed silicone polymer solution having a viscosity of 2,450 cps. The speed was set to about 100 rpm; the reactor heated to about 80 0 C and a vacuum was applied for about 30 minutes. Then, the vacuum was discontinued and the 10 nitrogen gas started. A monomer feed tank was charged with 102.2g of vinyl acetate, 517.6g of n-Butyl acrylate, 66.6g of methyl methacrylate, 3.3g of N-t-butyl acrylamide, and 13.7g of vinyl terminated siloxane polymer to provide a first 15 mixture. Catalyst was charged to a container with 1.47g of Lupersol 546-M75 and 0.84g of Lupersol 546-M75 to provide a second mixture. Then the first and second mixtures were WO99/31179 PCTIUS98/25988 -30 fed simultaneously to the reactor over a period of about three hours at about 80 0 C. Then the material was aged at 80 0 C for 30 minutes; then chaser a was added, and the composition was aged for about 30 minutes. Next chaser b 5 was added, and the temperature was raised to about 95 0 C, and the composition was aged for about 60 minutes. Next chaser c was added, the temperature was raised to about 110 0 C, and the composition was aged for about 60 minutes. Then vacuum was applied for about 30 minutes at about 110 0 C 10 and then the composition was cooled to about 75 0 C with the vacuum on, and then the dispersed copolymer polysiloxane composition was discharged. The viscosity of the resulting dispersed copolymer polysiloxane composition was about 240,000 cps as 15 measured on an HBT Brookfiled viscosometer using a number 6 spindle at 10 rpm. EXAMPLE 17 20 Example 17 was made as was Example 16, except that the N-t-butylacrylamide was not utilized.
WO 99/31179 PCT/US98/25988 -31 EXAMPLE 18 Formula (80/20)using 750 cps silicone polymer 1. Silicone Polymer Weight. gram , 750 cps silanol terminated polydimethylsiloxane 246 0.20003 2. Acrylic Monomers Vinyl acetate 143 0.11628 n-butyl acrylate 725 0.58951 Methyl methacrylate 93 0.07562 1000 cps vinyl terminated polydimethylsiloxane 19.2 0.01561 3. Initiators 546-M75 2.06 0.00168 575-M75 1.57 0.00128 TOTAL: 1229.83 1.00000 4. Chaser chaser a - 31 g Santicizer 160 and I g 575-M75 chaser b - 1 g 575-M75 Procedures Same as Example 16. except that this 80/20 formulation had 4 hour feed instead of 3 hour feed. In addition, the method of chaser is different as well. Here is the chasing method: 1. After 30 minutes 80 0 C aging. add chaser a and then raise temp. to 95 0 C and age for 60 min. 2. Add chaser b after 95 0 C aging, and then raise temp. to 1 10 0 C: age at I 10 0 C for 60 min. then vacuum for one hour. Polymer Properties: Viscosity = 344.000 cps: flow rate at 60 psi = 32.5 sec; particle size = 20-30 microns. Cured Properties (mixed with 4% MOS and 0.01% DBTDL) 1. Elongation = 350%. 100% modulus = 40 psi: tensile at break = 150 psi: hardness (Shore A) = 12. nft WO 99/31179 PCT/US98/25988 -32 EXAMPLE 19 5 A sealant composition suitable for use as a caulk, was prepared using the following ingredients: Material Total Charge Weight Percent Grams Example 16 (70% dispersed copolymer 30% 500 74.49 polydimethylsiloxane composition) Santicizer 160 plasticizer 67 9.98 Hydrophobic Treated Fumed Silica TS-720 0.65 0.10 Hydrophobic Treated Precipitated Calcium Carbonate (Socal 322) 25 3.72 Hydrophobic Treated Ground Calcium Carbonate 40 5.96 Pigment 6 0.89 Dimethylbis-secondary butylaminosilane 5.55 0.83 Methyltris-methylethylketoximosilane 19 2.83 Aminoethylaminopropyltrimethoxysilane 8.05 1.20 TOTALS 671.25 100.00 10 The dispersed copolymer polysiloxane composition of Example 16 was used to prepare the low modulus sealant composition from the above ingredients. First the fillers and reinforcing agents were incorporated into the dispersed copolymer polysiloxane composition of Example 16 under high 15 shear mixing conditions and vacuum in a changecan mixer, before the Santicizer 160 plasticizer was added. By first adding the fillers and reinforcing agents a maximum dispersion of the fillers was achieved. The dispersed copolymer polysiloxane composition 20 filler mixture and plasticizer were then mixed under vacuum at 100 ± 5SC for two hours to remove moisture from the precipitated calcium carbonate and the ground calcium carbonate. This mixture was then cooled below 50 0 C, and WO 99/31179 PCT/US98/25988 -33 then the moisture sensitive ingredients were added under dry nitrogen and mixed under vacuum for twenty minutes. Next the final sealant product was packaged. 5 EXAMPLE 20 A sealant composition suitable for use as a caulk, was prepared as in example 19, except that the following ingredients were used. Material Total Charge Weight Percent Example 16 copolymer-polydimethylsiloxane 500 74.48 composition Plasticizer- Santicizer 160 67 9.98 Hydrophobic Treated Fumed Silica TS-720 0.65 0.10 Hydrophobic Treated Precipitated Calcium Carbonate (Socal 322) 25 3.72 Hydrophobic Treated Ground Calcium Carbonate 40 5.96 Pigment 6 0.89 Dimethyl bis-secondary 5.55 0.83 Butylaminosilane Methyl tris-methyl 19 2.83 -ethylketoximosilane Aminoethylaminopropyltrimethoxysilane 8.05 1.20 Dibutyltindilaurate 0.05 0.01 TOTALS 671.30 100.00 10 WO 99/31179 PCTIUS98/25988 -34 EXAMPLE 21 A sealant composition suitable for use as a caulk, was prepared as in example 19, except that the following ingredients were used. 5 Material Total Charge Weight Percent Example 16 copolymer-polydimethylsiloxane 500 74.47 composition Santicizer 160 67 9.98 Hydrophobic Treated Fumed Silica TS-720 0.65 0.10 Hydrophobic Treated Precipitated Calcium Carbonate (Socal 322) 25 3.72 Hydrophobic Treated Ground Calcium Carbonate 40 5.96 Pigment 6 0.89 Dimethyl bis-secondary 5.55 0.83 Butylaminosilane (chain extender) Methyl tris-methyl- 19 2.83 Ethylketoximosilane (crosslinker) Aminoethylaminopropyltrimethoxysilane 8.05 1.20 (adhesion promoter) Dibutyltindilaurate (catalyst) 0.135 0.02 TOTALS 671.385 100.00 .... . ...... . .... . . - net € WO 99/31179 PCT/US98/25988 -35 EXAMPLE 22 A sealant composition suitable for use as a caulk, was prepared as in Example 19, except that the following ingredients were used in the amounts listed 5 below. Input Material Total Charge Weight Percent Example 16 500 61.70 (70-30 copolymer polydimethylsiloxane) composition) Santicizer 160 160 19.74 Hydrophobic Treated Precipitated Calcium Carbonate (Socal 322) 22.5 2.78 Hydrophobic Treated Ground Calcium 100 12.34 Carbonate Pigment (Titanium dioxide) 5 0.62 Methyl tris-methyl- 18 2.22 Ethylketoximosilane (crosslinker) Aminoethylaminopropyltrimethoxysilane 4.5 0.56 (adhesion promoter) Dibutyltindilaurate (catalyst) 0.3 0.04 TOTALS 810.3 100.00 The sealants of examples 19-22 were evaluated 10 without curing; the results are presented in Table V. Tooling life was measured using a round tip spatula at 25 0 C and 50% humidity, according to Mil-S-8802, sag was measured according to the Boeing sag flow in Mil-S-8802; extrusion rate was measured according to ASTM D-2254; and tack free 15 time was measured at according to the polyethylene release using a 25 gram weight according to Mil-S-8802. Examples 15-18 did not stain porous materials such as marble and are particularly desirable for use with such porous materials.
WO99/31179 PCTIUS98/25988 -36 Table V Properties of Uncured Sealants Example Sag Tooling Extrusion Tack (inch) Life Rate Free (min) (sec) Time (hours) 19 0.1 165 45 7 20 0.1 75 35 3.2 21 0.1 25 35 1.5 22 0 5.0 86 50 (min) 5 The sealants of examples 19-22 were coated, or more specifically drawn down, on a polyethylene sheets and cured at 25 0 C and 50% relative humidity for 21 days. The materials were then released from the polyethylene and 10 evaluated; shore A hardness was measured according to the Shore a Instrument test method according to in ASTM D-2240, tensile strength was measured using a Instron 20 inch/minute jaw separation rate according to ASTM D-412, modulus was measured using a Instron 20 inch/minute jaw 15 separation rate according to ASTM D-412, and elongation was measured using Instron 20 inch/minute jaw separation rate according to ASTM D-412. The results are presented in Table VI.
WO 99/31179 PCT/US98/25988 -37 Table VI Properties of Cured Sealants Example Shore A Tensile 100% Elongation % Hardness Strength Modulus (psi) (psi) 19 10 110 20 700 20 15 152 25 700 21 14 146 30 495 22 15 135 44 425 5 The sealant of Example 19-22 all demonstrated cohesive adhesion to glass, concrete limestone, marble and anodized aluminum substrates. No shrinkage was observed. Other suitable substrates for the sealants include, for 10 example, plastic, particularly polyacrylate, and rigid PVC, painted surfaces, wood, metal, stone, brick and other masonry materials. While in accordance with the Patent Statutes, the best mode and preferred embodiment has been set forth, the 15 scope of the invention is not limited thereto, but rather by the scope of the attached claims.
Claims (38)
1. An uncured copolymer-polysiloxane composition, comprising; 5 copolymer particles derived from monomers comprising at least a monomer capable of forming a low Tg polymer and at least a different monomer capable of forming a high Tg polymer, said copolymer particles being dispersed in reactive polysiloxane fluid, and 10 wherein the composition has a viscosity increase of less than 100% at 20 0 C after aging for 24 hours as measured by ASTM D2452-75.
2. An uncured copolymer-polysiloxane composition 15 according to Claim 1, wherein said monomers forming said copolymer particles are polymerized in the presence of said reactive polysiloxane fluid, wherein said low Tg is from about minus 70C to about 0 0 C, wherein said high Tg is from about 5 0 C to about 150 0 C, wherein the amount of said high Tg 20 polymer forming monomer is from about 2.5 to about 50 percent by weight and wherein the amount of said low Tg polymer forming monomer is from about 50 to about 97.5 percent by weight based upon the total weight of said copolymer derived from said low Tg and said high Tg polymer 25 forming monomers, and wherein the amount of said copolymer particles is from about 10 percent to about 85 percent by weight per 100 parts by weight of said polysiloxane fluid and said copolymer particles. 30
3. An uncured copolymer-polysiloxane composition according to Claim 2, wherein said polysiloxane has the formula WO99/31179 PCT/US98/25988 -39 R1 5 (R), 3 -m (X), Si-O Si- O Si (X), (R) 3 R 2 n wherein R 1 and R 2 , independently, is an alkyl having from 1 10 to 8 carbon atoms, an aromatic or an alkyl substituted aromatic having a total of from 6 to 10 carbon atoms, wherein n is such that the weight average molecular weight of the polysiloxane is from about 2,000 to about 200,000, wherein X, independently, is an OH group, or an OR 3 group, or 15 an N(R 4 ) 2 group, or CH 2 O ~II -- 0--C (enoxy), or -- O--C-R (acyloxy) 20 R 7 R 9 R n 11 -- O--N=C (oximo), or -- 0--N (aminoxy) 25 2R5 R12 RR 0 R s O 30 II or an -N-C-R 6 group, wherein R through R 2 , are, independently, an alkyl having from about 1 to about 8 carbon atoms, wherein each R group, independently, is an alkyl having from 1 to 8 carbon atoms or an aromatic or an 35 alkyl-aromatic having from 6 to 20 carbon atoms and optionally containing one or more functional groups, and wherein m is 1, 2, or 3, and wherein said viscosity increase after aging at viscosity increase after aging at 200C for 24 hours is less than 50 percent. 40
4. An uncured copolymer-polysiloxane composition according to Claim 3, wherein said low Tg polymer forming WO99/31179 PCT/US98/25988 -40 monomer is an alkyl acrylate wherein said alkyl group has from 1 to 8 carbon atoms, wherein said high Tg polymer forming monomer is a vinyl ester wherein the non-vinyl portion has from 2 to 10 carbon atoms, an acrylonitrile or 5 an alkyl derivative thereof wherein said alkyl group has from 1 to 6 carbon atoms, a vinyl substituted aromatic having a total of from 8 to 12 carbon atoms, or an alkyl methacrylate wherein said alkyl group has from 1 to 8 carbon atoms, or combinations thereof. 10
5. An uncured copolymer-polysiloxane composition according to Claim 4, wherein said low Tg polymer forming monomer comprises n-butyl acrylate, wherein said high Tg polymer forming monomer comprises said vinyl acetate, 15 wherein the amount of said low Tg polymer forming monomer is from about 60% to about 80% by weight based upon the total amount by weight of said low Tg and said high Tg polymer forming monomers, and wherein said viscosity increase is less than 25% at 200C after aging for 24 hours, and wherein 20 the amount of said copolymer particles is from about 50 to about 75 percent by weight.
6. An uncured copolymer-polysiloxane composition according to Claim 1, including a thixotropic agent and 25 optionally a compatibilizing agent.
7. An uncured copolymer-polysiloxane composition according to Claim 4, including a thixotropic agent and a compatibilizing agent. 30
8. A copolymer-polysiloxane composition according to Claim 1, wherein said copolymer particles are surface rich in said high Tg polymer, and wherein said composition is moisture cured. 35
9. A copolymer-polysiloxane composition WO 99/31179 PCT/US98/25988 -41 according to Claim 3, wherein said copolymer particles are surface rich in said high Tg polymer, wherein said composition is moisture cured, and wherein said composition has an elongation at break of at least 500 percent at 200C. 5
10. A copolymer-polysiloxane composition according to Claim 5, wherein said copolymer particles are surface rich in said high Tg polymer, and wherein said composition is moisture cured, and wherein said composition 10 has an elongation at break of at least 500 percent at 20 0 C.
11. A polysiloxane composition, comprising; a copolymer dispersed in a polysiloxane, said copolymer derived from monomers comprising at least a 15 monomer capable of forming a low Tg polymer and at least a different monomer capable of forming a high Tg polymer, said polysiloxane being cured and having an elongation at break of at least 300 percent at 20 0 C. 20
12. A polysiloxane composition according to Claim 11, wherein said monomers forming said copolymer are polymerized in the presence of said polysiloxane, wherein the amount of said high Tg polymer forming monomer is from about 2.5 to about 50 percent by weight and wherein the 25 amount of said low Tg polymer forming monomer is from about 50 to about 97.5 percent by weight based upon the total weight of all of said low Tg and said high Tg polymer forming monomers, wherein said polysiloxane has the formula 30 R (R) 3 m (X)m Si-O Si - 0 Si (X)m (R) 3 35 R 2 wherein R' and R 2 , independently, is an alkyl having from 1 WO99/31179 PCT/US98/25988 -42 to 8 carbon atoms, an aromatic or an alkyl substituted aromatic having a total of from 6 to 10 carbon atoms, wherein n is such that the weight average molecular weight of the polysiloxane is from about 2,000 to about 200,000, 5 wherein X, independently, is an OH group, or an OR 3 group, or an N(R 4 ) 2 group, or CH 2 0 --- C (enoxy), or ---- R 8 (acyloxy) 10R R 9 R 11 / / 15 --O--N=C (oximo), or --O--N (aminoxy) \l12 Rio R' 0 20 R s O or an -N-C-R 6 group, wherein R through R 12 , are, independently, an alkyl having from about 1 to about 8 carbon atoms, wherein each R group, independently, is an 25 alkyl having from 1 to 8 carbon atoms or an aromatic or an alkyl-aromatic having from 6 to 20 carbon atoms and optionally containing one or more functional groups, and wherein m is 1, 2, or 3, wherein said low Tg is from about minus 70 0 C to about 0 0 C, wherein said high Tg is from about 30 50C to about 1500C, wherein said low Tg polymer forming monomer is an alkyl acrylate wherein said alkyl group has from 1 to 8 carbon atoms, and wherein said high Tg polymer forming monomer is a vinyl ester wherein the non-vinyl portion has from 2 to 10 carbon atoms, an acrylonitrile or 35 an alkyl derivative thereof wherein said alkyl group has from 1 to 6 carbon atoms, or a vinyl substituted aromatic having a total of from 8 to 12 carbon atoms, or an alkyl methacrylate wherein said alkyl group has from 1 to 8 carbon atoms, or combinations thereof. WO99/31179 PCT/US98/25988 -43
13. A polysiloxane composition according to Claim 12, wherein said composition has a 100 percent tensile modulus of less than 50 psi, wherein the amount of said 5 copolymer is from about 10 percent to about 85 percent by weight per 100 parts by weight of said polysiloxane and said copolymer, wherein said high Tg forming monomer comprises said vinyl ester, and wherein said composition has an elongation at break of at least 300 percent at 20 0 C. 10
14. A polysiloxane composition according to Claim 11, including a thixotropic agent and optionally a compatibilizing agent, and wherein said copolymer is surface rich in said high Tg polymer. 15
15. A polysiloxane composition according to Claim 13, including a thixotropic agent and a compatibilizing agent, wherein said vinyl ester is vinyl acetate, wherein the amount of said copolymer is from about 50 about 75 20 percent by weight polymerized in the presence of said polysiloxane, and wherein said copolymer is surface rich in said high Tg polymer.
16. A process for forming a polysiloxane 25 composition, comprising the steps of; free radically polymerizing monomers comprising low and high Tg polymer forming monomers in the presence of a polysiloxane, wherein the amount of said low Tg polymer forming monomers is from about 50 percent to about 97.5 30 percent of said total monomers, wherein said low Tg is from about minus 70 0 C to about 0 0 C and wherein said high is from about 5 0 C to about 150 0 C.
17. A process according to Claim 16, wherein said 35 polysiloxane composition when cured has at 20 0 C an elongation WO99/31179 PCT/1US98/25988 -44 at break of at least 300 percent, wherein said low Tg polymer forming monomer is an alkyl acrylate wherein said alkyl group has from 1 to 8 carbon atoms, and wherein said high Tg polymer forming monomer is a vinyl ester wherein the 5 non-vinyl portion has from 2 to 10 carbon atoms, an acrylonitrile or an alkyl derivative thereof wherein said alkyl group has from 1 to 6 carbon atoms, a vinyl substituted aromatic having a total of from 8 to 12 carbon atoms, or an alkyl methacrylate wherein said alkyl group has 10 from 1 to 8 carbon atoms, or combinations thereof.
18. A process according to Claim 17, including adding a substantial amount by weight of a high Tg polymer forming monomer during a late polymerization stage or during 15 a second or subsequent polymerization stage.
19. A process according to Claim 18, wherein the amount of said low Tg polymer forming monomer is from about 60 to about 80 percent by weight, wherein the amount of said 20 copolymer is from about 100 to about 400 parts by weight per 100 parts by weight of said polysiloxane, and wherein said elongation of said polysiloxane composition when cured is at least 300 percent. 25
20. A process according to Claim 19, wherein said low Tg polymer forming monomer comprises n-butyl acrylate, and wherein said high Tg monomer comprises vinyl acetate.
21. A sealant, comprising: 30 from about 10 to about 85 percent by weight of a copolymer and from about 15 to about 90 percent by weight of a polysiloxane based upon the total weight of said copolymer and said polysiloxane, said copolymer derived from monomers comprising at least a monomer capable of 35 forming a low Tg polymer and at least a different monomer capable of forming a high Tg monomer; and WO99/31179 PCT/US98/25988 -45 based upon 100 parts by weight of said copolymer polysiloxane, from 0 to 15 parts by weight of an adhesion promoter; 5 from about 0.2 to about 20 parts by weight of a crosslinker; from 0 to about 100 parts by weight of a reinforcing agent; from 0 to 80 parts by weight of a plasticizer; 10 and, from about 0 to about 12 parts by weight of a chain extender.
22. The sealant of claim 21, wherein said low Tg 15 is from about minus 70*C to about 0OC, wherein said high Tg is from about 5 0 C to about 150 0 C, wherein the amount of said high Tg polymer forming monomer is from about 2.5 to about 50 percent by weight and wherein the amount of said low Tg polymer forming monomer is from about 50 to about 97.5 20 percent by weight based upon the total weight of said copolymer derived directly from said low Tg and said high Tg polymer forming monomers, and wherein the sealant when cured has an elongation at break of from about 250 to about 1,600 percent. 25
23. The sealant of claim 22, wherein the chain extender is present from about 0.2 percent to about 12 parts by weight. 30
24. The sealant composition of claim 23, wherein the reinforcing agent is present from about 0.1 to about 100 parts by weight, the plasticizer is present from about 5 to about 80 parts by weight, and wherein said elongation is from about 350 to about 1,400 percent. 35
25. The sealant of claim 24, wherein the WO99/31179 PCTIUS98/25988 -46 plasticizer is present from about 8 to 50 parts by weight, the reinforcing agent is present from about 0.1 to about 60 parts by weight, and the chain extender is present from about 0.2 to about 8 parts by weight. 5
26. The sealant of claim 24, wherein the plasticizer is a phthalate ester of butyl alcohol and benzyl alcohol the chain extender is dimethyl bis-secondary butylaminosilane, and the crosslinker is an oxime 10 crosslinker.
27. The sealant of claim 21, wherein there is: from about 0.75 to about 6 parts by weight of the 15 adhesion promoter; from about 1 to 10 parts by weight of the cross linker; from about 0.1 to 60 parts by weight of the reinforcing agent; 20 from about 8 to 50 parts by weight of the plasticizer; and from about 0.2 to about 8 parts by weight of the chain extender. 25
28. The sealant of claim 27, wherein the plasticizer is a phthalate ester of butyl alcohol and benzyl alcohol, the chain extender is dimethyl bis secondary butylaminosilane, the crosslinker is an oxime crosslinker, and the copolymer-polysiloxane composition is 30 the composition of claim 5.
29. The sealant of claim 27, wherein the plasticizer is a phthalate ester of butyl alcohol and benzyl alcohol, the chain extender is dimethyl bis 35 secondary butylaminosilane, the crosslinker is an oxime crosslinker, the adhesion promoter is aminopropyl- WO99/31179 PCT/US98/25988 -47 triethoxysilane or amino propyl trimethoxysilane, and the copolymer-polysiloxane is the composition of claim 5.
30. The sealant of claim 21, wherein the sealant 5 has a tool life of from about 20 to about 150 minutes.
31. The sealant of claim 24, wherein the dispersed copolymer-polysiloxane composition comprises about 70 percent of said copolymer and about 30 percent of 10 said polysiloxane; wherein said plasticizer comprises butyl benzyl phthalate; wherein said reinforcing agent comprises hydrophobic treated fumed silica or hydrophobic treated precipitated calcium carbonate; wherein said chain extender comprises dimethyl bis-secondary butylaminosilane; wherein 15 said crosslinker comprises methyl tris methylethylketoximosilane; and wherein said adhesion promoter is comprised of aminopropyltrimethoxysilane.
32. The sealant of claim 31, wherein said 20 catalyst is dibutyltin dilaurate.
33. The sealant of claim 21, having less than about a 1.0 inch sag, and a tooling life of at least about 5 minutes. 25
34. The sealant of claim 21, having less than about a 0.5 inch sag measured according to the Boeing sag flow in Mil-S-8802, and a tooling life of at least about 10 minutes measured using a round tip spatula at 25 0 C and 50% 30 humidity according to Mil-S-8802.
35. The sealant of claim 21, wherein said sealant when cured has a tack free time of less than about 12 hours measured according to the polyethylene release 35 method using a 25 gram weight according to Mil-S-8802. WO 99/31179 PCT/US98/25988 -48
36. The sealant of claim 21, wherein the sealant when cured has a Shore A hardness measured according to the Shore A Instrument test method of ASTM D-2240 of at least about 3, a tensile strength from about 20 to 400 psi 5 as measured using a Instron 20 inch/minute jaw separation rate according to ASTM D-412, an elongation at break of at least about 250 percent as measured using Instron 20 inch/minute jaw separation rate according to ASTM D-412, and an extension modulus at 100% elongation of least about 10 8 psi measured using a Instron 20 inch/minute jaw separation rate according to ASTM D-412.
37. The sealant of claim 21, wherein the sealant when cured has: a shore A hardness at least about 10 as 15 measured according to the Shore A Instrument test method of ASTM D-2240; a tensile strength of at least about 50 psi as measured using a Instron 20 inch/minute jaw separation rate according to ASTM D-412, an elongation of at least 350 percent as measured using an Instron 20 20 inch/minute jaw separation rate according to ASTM D-412; and a extension modulus at 100% elongation of less than about 50 psi as measured using a Instron 20 inch/minute jaw separation rate according to ASTM D-412. 25
38. A sealant coated substrate, comprising; a substrate, a cured sealant coated on the substrate, said cured sealant comprising: polymeric particles comprising polymerized 30 monomeric units of high Tg and polymerized monomeric units having a low Tg; polysiloxane; and, crosslinkers linking the polymeric particles.
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PCT/US1998/025988 WO1999031179A1 (en) | 1997-12-18 | 1998-12-08 | A polysiloxane having a copolymer dispersed therein and sealants containing the same |
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JP5462769B2 (en) * | 2010-11-17 | 2014-04-02 | 東レ・ダウコーニング株式会社 | Adhesive for wood, adhesion method using the adhesive, and composite using the adhesive |
CA2964866C (en) | 2016-04-20 | 2022-10-04 | Owens Corning Intellectual Capital, Llc | Hip and ridge/starter shingle combination |
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CN112111155B (en) * | 2019-06-19 | 2022-04-01 | 中国科学院化学研究所 | Blended polymer material of polyalkylmethacrylate and silicone rubber, preparation method and application thereof |
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-
1998
- 1998-12-08 DE DE1998606056 patent/DE69806056T2/en not_active Expired - Fee Related
- 1998-12-08 AT AT98962952T patent/ATE219125T1/en not_active IP Right Cessation
- 1998-12-08 BR BR9813632A patent/BR9813632A/en not_active IP Right Cessation
- 1998-12-08 EP EP19980962952 patent/EP1040165B1/en not_active Expired - Lifetime
- 1998-12-08 CA CA 2314959 patent/CA2314959C/en not_active Expired - Fee Related
- 1998-12-08 AU AU18077/99A patent/AU751067B2/en not_active Ceased
- 1998-12-08 CN CNB988123347A patent/CN1170888C/en not_active Expired - Fee Related
- 1998-12-08 KR KR1020007006632A patent/KR20010024737A/en not_active Application Discontinuation
- 1998-12-08 JP JP2000539090A patent/JP2002508426A/en not_active Withdrawn
- 1998-12-08 WO PCT/US1998/025988 patent/WO1999031179A1/en not_active Application Discontinuation
-
2000
- 2000-01-10 US US09/480,766 patent/US6403711B1/en not_active Expired - Lifetime
- 2000-06-16 NO NO20003136A patent/NO20003136L/en not_active Application Discontinuation
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EP1040165B1 (en) | 2002-06-12 |
WO1999031179A1 (en) | 1999-06-24 |
NO20003136L (en) | 2000-08-16 |
KR20010024737A (en) | 2001-03-26 |
DE69806056T2 (en) | 2003-01-23 |
JP2002508426A (en) | 2002-03-19 |
EP1040165A1 (en) | 2000-10-04 |
US6403711B1 (en) | 2002-06-11 |
CN1170888C (en) | 2004-10-13 |
AU751067B2 (en) | 2002-08-08 |
CA2314959A1 (en) | 1999-06-24 |
BR9813632A (en) | 2000-10-17 |
NO20003136D0 (en) | 2000-06-16 |
CA2314959C (en) | 2006-10-03 |
DE69806056D1 (en) | 2002-07-18 |
CN1282353A (en) | 2001-01-31 |
ATE219125T1 (en) | 2002-06-15 |
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